Method of making an alloy

ABSTRACT

A method of making an alloy comprises alloying components comprising: ferrosilicon having a ratio of iron to silicon; and at least one of a metallic element or a metallic compound. The alloy may be used in electrode compositions for lithium ion batteries.

TECHNICAL FIELD

The present disclosure broadly relates to methods for making metallicalloys.

BACKGROUND

Metallic alloys are used in negative electrodes for lithium ionbatteries. Negative electrodes containing such metal alloys generallyexhibit higher capacities relative to intercalation-type anodes such asgraphite. Typically, silicon-containing alloys are made directly fromthe respective component elements; for example, by a milling process.

Alloys containing Fe, Si, Sn, and/or C are useful, for example, asactive materials for use as a negative electrode material for a lithiumion battery. Small grain sizes of individual phases in such alloys aretypically important for good performance as an active electrode material(i.e., reversible lithiation/delithiation). This can typically beachieved by rapid quenching (e.g., melt spinning or sputtering), ormilling (e.g., mechanical alloying).

Current common practice in the industry uses powdered purified elementalmetals as raw materials to fabricate active electrode materials usingprocesses that are typically laborious, time-consuming, and/or costly.

SUMMARY

In one aspect, the present disclosure provides a method of making analloy, the method comprising alloying components comprising:

a first ferrosilicon having a first ratio of iron to silicon; and

at least one of a metallic element or a metallic compound, wherein thealloy is substantially free of crystallites greater than 50 nanometersin size. Alloys prepared according to the present disclosure may besuitable for use as a negative electrode material in a lithium ionbattery.

In some embodiments, the metallic element or metallic compound comprisesat least one of carbon, tin, titanium, zinc, iron, or silicon. In someembodiments, the alloy is amorphous. In some embodiments, alloyingcomprises milling using milling media. In some embodiments, the alloycomprises tin, iron, and silicon. In some embodiments, the alloycomprises tin, iron, and carbon.

In some embodiments, the metallic compound comprises a secondferrosilicon having a second ratio of iron to silicon, and wherein thefirst ratio and the second ratio are different.

Advantageously, alloys prepared according to the present disclosure cantypically be prepared easier, faster, and less expensively than withconventional processes that use pure forms of the components used tomake the alloy. In part, this is because some grades of ferrosilicon(e.g., iron containing 50, 75, and 90 percent by weight of silicon) arecommercially available by the ton at relatively low prices. Manydifferent grades of ferrosilicon are readily available commercially.

As used herein:

the term “alloy” refers to a substance having one or more metallicphases, and comprising two or more metallic elements;

the term “alloying” refers to a process that forms an alloy;

the term “delithiation” refer to a process for removing lithium from anelectrode material;

the term “metallic” means of, relating to, or having the characteristicsof a metal;

the term “metallic compound” refers to compounds that include at leastone metallic element;

the term “metallic element” refers to all elemental metals (includingtin), silicon, and carbon;

the term “mill” refers to a device for alloying, grinding, pulverizing,or otherwise breaking down a material into small particles (examplesinclude pebble mills, jet mills, ball mills, rod mills and attritormills);

the term “milling” refers to a process of placing a material in a milland operating the mill to perform alloying, or to grind, pulverize, orbreak down the material into small or smaller particles; and

the term “negative electrode” refers to an electrode of a lithium ionbattery (often called an anode) where electrochemical oxidation anddelithiation occurs during a discharging process.

DETAILED DESCRIPTION

Ferrosilicon is a metallic alloy of iron and silicon commonly preparedby fusing iron and silica in the presence of carbon in an electricfurnace. It is of considerable importance in the manufacture of steeland cast iron. Accordingly, ferrosilicon is available commercially invarious weight ratios of iron to silicon covering essentially the entirecompositional range. Examples include 0.1:99, 1:99, 5:95, 10:90, 20:80,30:70, 40:60, 50:50, 60:40, 70:30, 80:20, 90:10, 95:5, 99.9:0.1,although other ratios may also be used. Ferrosilicon with thecompositions 50:50 (Fe:Si by weight) and 25:75 (Fe:Si by weight) arewidely available in tonnage quantities, and at commodity prices that maybe less that the constituent purified metallic elements (i.e., iron andsilicon).

According to the present disclosure, at least one ferrosilicon isalloyed with at least one metallic element and/or metallic alloy. Themetallic alloy may be any metallic alloy; for example, a ferrosilicon,an alloy of silicon and tin, or an alloy of carbon and iron. In thoseembodiments of the present disclosure using two compositionallydifferent ferrosilicon alloys, it is possible to achieve anycompositional ratio of iron to silicon that falls between thecompositional ratios of the two ferrosilicon alloys. For example, using50:50 Fe:Si and 25:75 Fe:Si ferrosilicon alloys, it is possible toachieve all compositional ranges between 50 and 75 percent silicon byblending appropriate amounts of each. For values lying outside thecorresponding range, pure elemental iron or silicon may be added in anamount that achieves a desired stoichiometry.

Additional metallic elements and metallic alloys may optionally beincorporated in processes according to the present disclosure, may bereadily obtained from commercial sources. Examples include carbon,silicon, tin, and transition metals (e.g., Fe, Ti, Y, V, Cu, Zr, Zn, Co,Mn, Mo, and Ni), and alloys thereof, although other metallic elementsand metallic alloys may also be used.

Alloying may be conducted thermally; for example, in an electric arcfurnace. Alloying may also be accomplished by mechanical methods suchas, for example, milling. The alloying process may use ingot, chunk,powder, or other forms of ferrosilicon and optional metallic componentsto be included in that alloy.

Milling techniques are generally useful for mechanically alloyingmetallic elements and/or metallic alloys; especially as powders.Examples of suitable milling techniques include jet milling, ballmilling (e.g., using a planetary mill, vibrational mill, attritor mill,or a cylindrical or conical vessel). Jet mills abrade particles byimpinging them against hard target substrates. Ball mills containmilling media that serve to grind material placed in the mill. Examplesof suitable milling media include steel, porcelain, and/or ceramicmedia, which may be in the form of rods, balls, or other shapes. Ingeneral, the process conditions will vary with the type of millingtechnique used, and will be apparent to those of ordinary skill in themilling art.

In general, milling should be conducted in a controlled oxygenenvironment; for example, in an inert gas (e.g., nitrogen, helium,and/or argon) environment. In general, the use of preformed metallicalloys significantly reduces the processing time required for formingdesired alloys as compared to using pure metallic elements. For example,methods according to the present disclosure are especially useful formechanically alloying metallic element powders and/or metallic alloypowders.

Mechanically alloyed compositions prepared according to the presentdisclosure are useful, for example, for forming electrode compositions(e.g., negative electrode compositions) for use in lithium ionbatteries.

It may be desirable to use milling conditions that result in few if anycrystallites of significant size being present in the resultant alloy.For example, the resultant alloy may be formed such that it issubstantially free of crystallites greater than 50 nanometers in size(i.e., the maximum dimension of each crystallite). The resultant alloymay contain less than 5 percent by volume, less than one percent byvolume, or even less than 0.1 percent by volume of crystallites greaterthan 50 nanometers in size. In some embodiments, the resultant alloy maybe formed as an amorphous composition.

One desirable method of mechanically alloying metallic elements and/ormetallic alloys is described in U.S. application Ser. No. ______,entitled “LOW ENERGY MILLING METHOD, ALLOY, AND NEGATIVE ELECTRODECOMPOSITION” (Attorney Docket No. 65465US002), filed contemporaneouslyherewith.

Exemplary alloys include silicon alloys wherein the active materialcomprises from about 50 to about 85 mole percent silicon, from about 5to about 25 mole percent iron, from about 0 to about 12 mole percenttitanium, and from about 0 to about 12 mole percent carbon. Exemplaryalloys of silicon, iron and additional elements may be found in, forexample,

U.S. Pat. Appl. Publ. Nos. 2005/0031957 A1 (Christensen et al),2007/0020521 A1 (Obrovac et al.), and 2007/0020522 A1 (Obrovac et al.).

If mechanical alloying is used, a milling aid may optionally be added tothe metallic components being alloyed. Examples of milling aids includeone or more saturated higher fatty acids (e.g., stearic acid, lauricacid, and palmitic acid) and salts thereof, hydrocarbons such as mineraloil, dodecane, polyethylene powder. In general the amount of anyoptional milling aid is less than 5 percent, typically less than 1percent of the millbase.

Objects and advantages of this disclosure are further illustrated by thefollowing examples, but the particular materials and amounts thereofrecited in these examples, as well as other conditions and details,should not be construed to unduly limit this disclosure.

EXAMPLES

Unless otherwise noted, all parts, percentages, ratios, etc. in theExamples and the rest of the specification are by weight.

The following Abbreviations are used in the Examples.

ABBRE- VIATION DESCRIPTION DEC Diethyl carbonate from Ferro Corp. ECEthylene carbonate from Ferro Corp., Zachary, LA Fe1 Iron pieces havingirregular shape with a size 12 mm or less, 99.97 percent pure, availablefrom Alfa Aesar. FEC Fluoroethylene carbonate from Fujian ChuangxinScience and Develops Co., LTD, Fujian, China FerroSi50 Ferrosiliconcontaining 47.92 percent of silicon and 51.35 percent of iron availablefrom Globe Metallurgical, Inc. Crushed and sized to less than 500micrometers. FerroSi75 Ferrosilicon containing 73.53 percent of siliconand 24.88 percent by weight of iron available from Globe Metallurgical,Inc., Beverly, OH. Crushed and sized to less than 500 micrometers.Graphite1 A graphite powder available as TIMREX SFG44 from TIMCAL Ltd.,Bodio, Switzerland. Graphite2 A graphite powder with an average particlesize of 24.4 micrometers and a 3.2 m²/g BET surface area available asMAGE from Hitachi Chemical Co. Ltd., Tokyo, Japan LiOH-20 A 20 percentsolution of lithium hydroxide in water, prepared from LiOH—H₂O anddeionized water. LiOH—H₂O Lithium hydroxide monohydrate, 98+%, A.C.S.Reagent available from Sigma-Aldrich Co, St. Louis, MO. PAA-34 Apolyacrylic acid solution having a weight average molecular weight of250,000 g/mole available as a 34 percent solution in water fromSigma-Aldrich Co. PAA-Li A 10 percent polyacrylic acid - lithium saltsolution in water prepared by titrating PAA-34 with LiOH-20 until fullyneutralized and adding deionized water to obtain the desired 10 percentconcentration. Si1 Silicon pieces with a size of 10 cm or less, 98.4percent pure, available from Alfa Aesar, Ward Hill, MA. Sn1 325 mesh tinpowder, 99.8 percent pure, available from Alfa Aesar. Ti1 325 meshtitanium powder, 99.5 percent pure, available from Alfa Aesar.

X-Ray Measurement

X-ray diffraction patterns were collected using a Siemens ModelKRISTALLOFLEX 805 D500 diffractometer equipped with a copper targetx-ray tube and a diffracted beam monochromator. The X-ray diffractionpatterns were collected using scattering angles between 20 and 60degrees [two-theta] stepped at 0.05 degrees [two-theta]. The crystallinedomain size was calculated from the width of x-ray diffraction peaksusing the Scherrer equation.

Comparative Example A

Large grain SiFe alloy was prepared by arc melting 120.277 grams (g) ofSi1 and 79.723 g of Fe1. The Si₇₅Fe₂₅ ingot, containing about 75 molepercent silicon and 25 mole percent iron, was crushed and sized to lessthan 150 micrometers. The Si/Fe large grain alloy powder (120 g), wasplaced in the 5 liter, steel chamber of a ball mill (Model 611, Jar size1 available from U.S. Stoneware, Ohio). The chamber was cylindrical inshape with an internal diameter of about 18.8 cm (7.4 inch) and a lengthof about 17.1 cm (6.75 inch). In addition to the large grain alloypowder, 10 kg of 1.27 cm (0.5 inch) diameter chromium steel balls, onecylindrical steel bar 23.2 cm (9.125 inch) length×1.27 cm (0.5 inch)diameter and two cylindrical steel bars 21.5 cm (8.625 inch) length×1.27cm (0.5 inch) diameter were added to the chamber. The chamber was purgedwith N₂ and milled at 85 rpm (revolutions per minute) for 6 days. Aftermilling, a Si/Fe powder alloy containing about 75 mole percent siliconand 25 mole percent iron was produced (Powder A).

An X-ray diffraction pattern of the Si₇₅Fe₂₅ alloy ingot showedcrystalline Si and crystalline FeSi₂. An X-ray diffraction pattern ofPowder A showed nanostructures with small grain size for the FeSi₂ phaseand a virtually amorphous Si phase. The term “amorphous” is used in theExamples to describe materials that have no defined X-ray diffractionpeak indicative of a crystalline phase.

Example 1

FerroSi75 (59.27 g) and FerroSi50 (72.15 g) were milled used theprocedure described in Comparative Example A, except the milling timewas 7 days. After milling, a Si/Fe alloy powder containing about 75 molepercent silicon and 25 mole percent iron was produced, Powder 1. TheX-ray diffraction pattern of the starting FerroSi75 showed peakscharacteristic of crystalline Si and FeSi₂ phases. The X-ray diffractionpattern of the starting FerroSi50 showed peaks characteristic ofcrystalline FeSi₂ phases with small trace of crystalline Si. The x-raydiffraction pattern of Powder 1 showed peaks characteristic ofnanocrystalline FeSi₂ having a grain size less than 50 nm. The X-raydiffraction pattern of Powder 1 did not contain peaks from Si,indicating that the Si phase in the ball milled alloy was amorphous.

Example 2

FerroSi75 (83.74 g), 45.55 g of FerroSi50, and 2.38 g of Graphite1 weremilled using the procedure described in Comparative Example A, exceptthe milling time was 9 days. After milling, a Si/Fe/C alloy powdercontaining about 75 mole percent silicon, 20 mole percent iron and 5mole percent carbon was produced, Powder 2. The X-ray diffractionpattern of Powder 2, showed peaks characteristic of nanocrystallineFeSi₂ with a grain size less than 50 nm. The X-ray diffraction patternof Powder 2 did not contain peaks from Si, indicating that the Si phasein the alloy was amorphous. From stoichiometry, this alloy alsocontained a SiC phase, however, the X-ray diffraction pattern of theball milled alloy did not contain peaks from SiC, indicating that thisphase was amorphous.

Example 3

FerroSi75 (111.70 g), 15.08 g of FerroSi50, and 5.10 g of Graphite1 weremilled using the procedure described in Example 2. After milling, aSi/Fe/C alloy powder containing about 75 mole percent silicon, 15 molepercent iron and 10 mole percent carbon was produced, Powder 3. Thex-ray diffraction pattern of Powder 3 showed peaks characteristic ofnanocrystalline FeSi₂ with a grain size less than 50 nm. The x-raydiffraction pattern of Powder 3 did not contain peaks from Si,indicating that the Si phase in the alloy was amorphous. Fromstoichiometry, this alloy also contained a SiC phase, however, the X-raydiffraction pattern of the alloy did not contain peaks from SiC,indicating that this phase was amorphous.

Example 4

FerroSi75 (46.21 g), 69.06 g of FerroSi50, and 15.97 g of Sn1 weremilled using the procedure described in Comparative Example A. Aftermilling, a Si/Fe/Sn alloy powder containing about 71 mole percentsilicon, 25 mole percent iron and 4 mole percent tin was produced,Powder 4. The X-ray diffraction pattern of Powder 4 showed peakscharacteristic of nanocrystalline FeSi₂ with a grain size less than 50nm. The x-ray diffraction pattern of Powder 4 did not contain peaks fromSi and Sn, indicating that the Si and Sn phases in the ball milled alloywere amorphous.

Example 5

FerroSi75 (46.02 g), 62.82 g of FerroSi50, 16.89 g of Sn1, and 4.27 g ofGraphite 1 were placed in the chamber of the ball mill described inComparative Example A. Milling used the procedure described inComparative Example A. After milling, a Si/Fe/Sn/C alloy powdercontaining about 64 mole percent silicon, 22 mole percent iron, 4 molepercent tin and 10 mole percent carbon was produced, Powder 5. The X-raydiffraction pattern of Powder 5 showed peaks characteristic ofnanocrystalline FeSi₂ with a grain size less than 50 nm. The X-raydiffraction pattern of Powder 5 did not contain peaks from Si, Sn andSiC, indicating that the Si, Sn and SiC phases in the alloy wereamorphous.

Example 6

FerroSi75 (64.29 g), 42.77 g of FerroSi50, 16.14 g of Sn1, and 8.14 g ofTi1 were milled using the procedure described in Comparative Example A,except the milling time was 13 days. After milling, a Si/Fe/Sn/Ti alloypowder containing about 71 mole percent silicon, 20 mole percent iron, 4mole percent tin and 5 mole percent titanium was produced, Powder 6. TheX-ray diffraction pattern of Powder 6, showed peaks characteristic ofnanocrystalline FeSi₂ with a grain size less than 50 nm. The X-raydiffraction pattern of Powder 6 did not contain peaks from Si, Sn andTiSi₂ (and/or FeTiSi₂), indicating that the Si, Sn and TiSi₂ (and/orFeTiSi₂) phase alloy were amorphous.

Example 7

FerroSi75 (1.27 g), 0.69 g of FerroSi50, and 0.04 g of Graphite1 wereplaced in a 45-milliliter tungsten carbide chamber, Model 8001 from SpexCertiprep Ltd., Metuchen, N.J. In addition to the powder, 28 tungstencarbide balls (about 108 g) having a 0.79 cm (0.3125 inch) diameter wereadded to the chamber. The chamber was placed in a dual mixer/mill, Model8000-D from Spex Certiprep Ltd. The chamber was vibrated by the dualmixer/mill for two hours. The vessel was cooled with an air jet duringthe two hour milling period, maintaining a chamber temperature of about30° C. After milling, a Si/Fe/C alloy powder containing about 75 molepercent silicon, 20 mole percent iron, and 5 mole percent carbon wasproduced, Powder 7. The x-ray diffraction pattern of Powder 7 showedpeaks characteristic of nanocrystalline Si and FeSi₂ with a grain size 6nm and 12 nm, respectively. From stoichiometry, this alloy alsocontained SiC phases, however, the X-ray diffraction pattern of Powder 7did not contain peaks from SiC, indicating that this phase wasamorphous.

Example 8

FerroSi75, 1.70 g, and FerroSi50, 0.23 g and 0.08 g Graphite 1 weremilled using the procedure described in Example 7. After milling, aSi/Fe/C alloy powder containing about 75 mole percent silicon, 15 molepercent iron and 10 mole percent carbon was produced, Powder 8. Thex-ray diffraction pattern of Powder 8 showed peaks characteristic ofnanocrystalline Si and FeSi₂ with a grain size of 11 nm and 12 nm,respectively. From stoichiometry, this alloy also contained a SiC phase,however, the X-ray diffraction pattern of Powder 8 did not contain peaksfrom SiC, indicating that this phase was amorphous.

Procedure for Preparing an Alloy Electrode, Cell Assembly and CellTesting

Alloy powder (1.84 g) and 1.6 g of PAA-Li were mixed in a 45-milliliterstainless steel vessel using four, 1.27 cm (0.5 inch) tungsten carbideballs. The mixing was done in a Planetary Micro Mill Pulverisette 7 fromFritsch, Germany at speed 2 for one hour. The resulting solution washand spread onto a 10-micrometer thick Cu foil using a gap die(typically 3 mil gap). The sample was then dried in a vacuum oven at120° C. for 1-2 hours producing an alloy electrode film. Circles, 16 mmin diameter, were then punched out of the alloy electrode film and wereused as an alloy electrode for a cell (below).

Half coin cells were prepared using 2325 button cells. All of thecomponents were dried prior to assembly and the cell preparations weredone in a dry room with a −70° C. dew point. The cells were constructedfrom the following components and in the following order, from thebottom up. Cu Spacer/Li metal film/Separator/alloy electrode/Cu spacer.Each cell consisted of a 20 mm diameter×0.762 mm (30 mil) thick disk ofCu spacer, a 16 mm diameter disk of alloy electrode, a 20 mm diametermicro porous separators (CELGAR2400p available from Separation Products,Hoechst Celanese Corp., Charlotte, N.C.), 18 mm diameter×0.38 mm thickdisk of Li metal film (lithium ribbon available from Aldrich ChemicalCo., Milwaukee, Wis.) and a 20 mm diameter×0.762 mm (30 mil) disk ofcopper spacer. The electrolyte was a solution containing 90 percent byweight of an EC/DEC solution (2/1 by volume) and 10 percent by weightFEC with LiPF₆ used as the conducting salt at a 1 M concentration. Priorto adding the LiPF₆, the mixture was dried over molecular sieve (3Atype) for 12 hours. The cell was filled with 100 microliters ofelectrolyte solution. The cell was crimp sealed prior to testing.

Cells were cycled from 0.005V to 0.90V at specific rate of 100mA/g-alloy with trickle down to 10 mA/g at the end of discharge(delithiation) for the first cycle. From then on, cells were cycled inthe same voltage range but at 200 mA/g-alloy and trickle down to 20mA/g-alloy at the end of discharge. Cells were allowed 15 min rest atopen circuit at the end of every half cycle.

Example 9

An alloy electrode film and three coin cells were prepared and testedaccording to the Procedure for Preparing an Alloy Electrode, CellAssembly and Cell Testing using Powder 1. Results are reported Table 1.

Example 10

An alloy electrode film and three coin cells were prepared and testedaccording to the Procedure for Preparing an Alloy Electrode, CellAssembly and Cell Testing using Powder 4. Results are reported Table 1.

Example 11

An alloy electrode film and three coin cells were prepared and testedaccording to the Procedure for Preparing an Alloy Electrode, CellAssembly and Cell Testing using Powder 5. Results are reported Table 1.

Example 12

An alloy electrode film and three coin cells were prepared and testedaccording to the Procedure for Preparing an Alloy Electrode, CellAssembly and Cell Testing using Powder 6. Results are reported Table 1.

Example 13

An alloy electrode film was prepared using Powder 4. Powder 4 was firstsized by milling in heptane. Powder 4 (4 g) and 20 g of heptane wereplaced in a 45-milliliter stainless steel vessel containing 17.62 g of9.5 mm (0.375 inch) diameter chromium steel balls and 22.98 g of 6.35 mm(0.25 inch) diameter chromium steel balls. The milling was done in aPlanetary Micro Mill Pulverisette 7 at a speed 5 for one hour. Excessheptane was removed, and the wet sample was dried at 80° C. for 1 hour.An alloy electrode film was prepared from the sized powder in thefollowing manner. Sized Powder 4 (0.96 g), 0.96 g of Graphite2, 0.8 g ofPAA-Li, and 4.5 g of deionized water, were mixed in a 45-milliliterstainless steel vessel using four 12.7 mm (0.5 inch) diameter tungstencarbide balls. The mixing was done in the Planetary Micro MillPulverisette 7 at speed 2 for one hour. The resulting solution was handspread onto a 10-micrometer thick Cu foil using an 8-mil gap die. Thesample was air dried, then calendered and dried in a vacuum oven at 120°C. for 1 hour. Circles, 16 mm in diameter, were then punched out of thealloy electrode film and were used as an alloy electrode for a cell.Three coin cells were prepared according to the second paragraph of theProcedure for Preparing an Alloy Electrode, Cell Assembly and CellTesting. The cells were cycled from 0.005 V to 0.90 V at specific rateof 75 mA/g-alloy with trickle down to 7.5 mA/g at the end of discharge(delithiation) for the first cycle. From then on, cells were cycled inthe same voltage range but at 150 mA/g-alloy and trickle down to 15mA/g-alloy at the end of discharge. Cells were allowed 15 min rest atopen circuit at the end of every half cycle. Results are reported inTable 1 (below).

TABLE 1 Initial Capacity Capacity at Capacity at Loss, Cycle 2, Cycle50, Efficiency Example percent mAh/g mAh/g percent 9 11 912 895 98 10 13818 763 93 11 13 861 752 87 12 14 875 865 99 13 16 554 544 98 In Table 1(above), Efficiency = Capacity at Cycle 50/Capacity at Cycle 2.

Overall, the alloy powders prepared according to the present disclosure,when fabricated into an electrode and further fabricated into a cell,showed stable capacity for many cycles, making them suitable for use asactive anode materials in battery applications, including rechargeablelithium ion battery applications.

All patents and publications referred to herein are hereby incorporatedby reference in their entirety. All examples given herein are to beconsidered non-limiting unless otherwise indicated. Variousmodifications and alterations of this disclosure may be made by thoseskilled in the art without departing from the scope and spirit of thisdisclosure, and it should be understood that this disclosure is not tobe unduly limited to the illustrative embodiments set forth herein.

1. A method of making an alloy, the method comprising alloyingcomponents comprising: a first ferrosilicon having a first ratio of ironto silicon; and at least one of a metallic element or a metalliccompound, wherein the alloy is substantially free of crystallitesgreater than 50 nanometers in size.
 2. The method of claim 1, whereinsaid metallic element or metallic compound comprises at least one ofcarbon, tin, titanium, zinc, iron, or silicon.
 3. The method of claim 1,wherein the alloy is amorphous.
 4. The method of claim 1, whereinalloying comprises milling using milling media.
 5. The method of claim1, wherein the alloy comprises tin, iron, and silicon.
 6. The method ofclaim 1, wherein the alloy comprises tin, iron, and carbon.
 7. Themethod of claim 1, wherein the metallic compound comprises a secondferrosilicon having a second ratio of iron to silicon, and wherein thefirst ratio and the second ratio are different.
 8. The method of claim7, wherein the components further comprise tin.
 9. The method of claim7, wherein the components further comprise titanium.
 10. The method ofclaim 1, wherein the alloy is adapted for use as an active material in anegative electrode composition in a lithium ion battery.
 11. The methodof claim 10, wherein said metallic element or metallic compoundcomprises at least one of carbon, tin, titanium, zinc, iron, or silicon.12. The method of claim 10, wherein the alloy is amorphous.
 13. Themethod of claim 10, wherein alloying comprises milling using millingmedia.
 14. The method of claim 10, wherein the alloy comprises tin,iron, and silicon.
 15. The method of claim 10, wherein the alloycomprises tin, iron, and carbon.
 16. The method of claim 10, wherein thecomponents further comprise a second ferrosilicon having a second ratioof iron to silicon, and wherein the first ratio and the second ratio aredifferent.
 17. The method of claim 16, wherein the components furthercomprise tin.
 18. The method of claim 16, wherein the components furthercomprise titanium.